Process for catalytic oxidation of olefins to form hydroperoxides

Abstract

Polymeric complexes formed between a thermally-condensed polyacrylonitrile polymer and transition metal salts, including rare earth metals, have been found to be effective catalysts for the oxidation of compounds containing activated carbon-hydrogen bonds such as olefins, or secondary and tertiary alkylaromatics, to form valuable oxidation products, particularly hydroperoxides or their decomposition products.

The invention claimed is: 
     
       1. In the process for the catalytic oxidation of aliphatic or alicyclic olefins having at least one hydrogen atom on the α-carbon atom, said olefins having from 3 to 18 carbon atoms, or secondary or tertiary alkylaromatic hydrocarbons of the formula ##STR5## wherein R is lower alkyl; R 1  is lower alkyl or hydrogen; and Ar is an aromatic nucleus selected from the group consisting of phenyl and naphthyl, in the presence of air or oxygen at a temperature of from about 80° to 200° C. to form hydroperoxides, the decomposition products thereof, or mixtures of the same, the improvement wherein the catalyst is a polymeric complex formed from a thermally condensed polyacrylonitrile and a transition metal salt, wherein said transition metal is from Group IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIIIB, or IIA of the Periodic Table and wherein the ratio of said catalyst to said olefin or alkylaromatic hydrocarbon is from about 0.01 to 5.0 parts by weight of catalyst per 100 parts by weight of olefin or alkylaromatic hydrocarbon. 
     
     
       2. The process according to claim 1 wherein the metal of the metal salt is of the lanthanide or actinide series of the Periodic Table. 
     
     
       3. The process according to claim 1 wherein the alkylaromatic compound is cumene and the product consists substantially of cumyl hydroperoxide. 
     
     
       4. The process according to claim 1 wherein the oxidation is carried out in the added presence of an hydroperoxide initiator. 
     
     
       5. The process according to claim 1 wherein the ratio of catalyst to olefin is in the range of from 0.2 to 1.0 parts by weight of catalyst per 100 parts of olefin. 
     
     
       6. The process according to claim 1 wherein the reaction is carried out under vigorous agitation. 
     
     
       7. The process according to claim 1 wherein the oxygen is introduced at a rate of from about 0.5 to 300 liters per hour. 
     
     
       8. The process according to claim 1 wherein the oxidation is carried out at an oxygen pressure of from 1 to 50 atmospheres. 
     
     
       9. The process according to claim 1 wherein the anion is a bromide, chloride, carbonate, nitrate or perchlorate. 
     
     
       10. The process according to claim 1 wherein the anion is a cyanide, cyanate, isocyanate, nitrite, phosphate, acetate, or oxalate. 
     
     
       11. The process according to claim 1 wherein the hydroperoxide decomposition products are alcohols, aldehydes, ketones, or mixtures thereof. 
     
     
       12. The process according to claim 1 wherein the salt is a nickel, copper, or cobalt salt. 
     
     
       13. The process according to claim 1 wherein the thermally-condensed polyacrylonitrile metal salt catalyst is formed by the heating of an excess by weight to the metal salt of the homopolymeric polyacrylonitrile at temperatures of from about 200° to 400° C. in the presence of said metal salt.